CN102910614A - Method for heterogeneous epitaxial growth of graphene - Google Patents
Method for heterogeneous epitaxial growth of graphene Download PDFInfo
- Publication number
- CN102910614A CN102910614A CN2011102221912A CN201110222191A CN102910614A CN 102910614 A CN102910614 A CN 102910614A CN 2011102221912 A CN2011102221912 A CN 2011102221912A CN 201110222191 A CN201110222191 A CN 201110222191A CN 102910614 A CN102910614 A CN 102910614A
- Authority
- CN
- China
- Prior art keywords
- graphene
- growth
- vapor deposition
- chemical vapor
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention provides a method for heterogeneous epitaxial growth of graphene. Graphene grows on a single crystal substrate in an epitaxial mode by utilizing a plasma-enhanced chemical vapor deposition method, wherein the lattices of the single crystal substrate are matched with the lattices of the graphene. According to the method for heterogeneous epitaxial growth of graphene, the graphene can grow at low temperature, a catalyst does not need to be adopted, and the epitaxial single crystal graphene with a perfect lattice quality can be formed.
Description
Technical field
The present invention relates to a kind of method of heteroepitaxial growth Graphene.
Background technology
Graphene is by sp
2The hydridization carbon atom bonding, and have the individual layer plane graphite of the cellular two-dirnentional structure of hexagonal lattice, have high crystal quality and electric property.As a kind of strict two dimensional crystal material, Graphene has unique physicals, and carrier concentration is up to 10
13Cm
-2, mobility surpasses 2 * 10
5Cm
2V
-1s
-1, for the preparation of transistor, sensor high performance device provides the material foundation stone to go out.
The way that the reported first of Graphene is the A.K.Geim of Univ Manchester UK in 2004 professor study group by machinery can successfully strip down from graphite.Method by mechanically peel is peeled off the graphite flake that can obtain individual layer layer by layer from graphite, i.e. Graphene.The Graphene area that this method obtains is little, cost is high, only can be used for fundamental research, is not suitable for the integrated of device, has limited its application.Therefore, the controlled preparation of high quality, big area Graphene is the major issue of Graphene research field.
Aspect the preparation of high quality, big area Graphene, mainly contain at present three kinds of growth methods: one, chemical Vapor deposition process (CVD), this method is at the Polycrystalline Metals film with catalytic performance of substrate surface deposition one deck tens nanometer thickness (for example: Ni to utilize, Cu etc.), then utilize thermocatalysis to decompose hydrocarbon polymer (as: CH
4, C
2H
2Deng) next surface growth Graphene at metallic film; Two, high temperature annealing SiC epitaxial method, this method are that the way of utilizing high temperature (～1350 ℃) to process evaporates surperficial Siliciumatom, stay carbon atom, form Graphene; Three, metal single crystal surface epitaxial method, similar with method one, catalyzer is the metal single crystal with catalytic performance, then utilize separating out or thermocatalysis decomposition hydrocarbon polymer of crystals carbon impurity, at the surperficial epitaxial graphite alkene of metal single crystal, and method one difference is that the lattice of the Graphene of growing and the lattice of metal single crystal are complementary.
Yet, more than three kinds of methods separately limitation is arranged.The Graphene of method one growth is that the Graphene polycrystalline by random orientation is bonded with each other and forms continuous thin film together, there are a lot of crystal boundaries, the existence of the Nonuniform orientation of Graphene polycrystalline and a large amount of crystal boundaries, can destroy mechanics and the electric property of Graphene, also can bring a lot of problems to its application.The method two growing graphene needs very high temperature, brings a lot of problems to actual industrial production, and on the other hand, the Graphene of preparation is also inhomogeneous, and major part is single-layer graphene, and quite a few is also arranged is two-layer or three layers Graphene.Method three is difficult to the preparation of growing in enormous quantities.
Summary of the invention
Therefore, the object of the invention is to overcome the defective of above-mentioned prior art, a kind of method of heteroepitaxial growth Graphene is provided, can grow at low temperatures, needn't adopt catalyzer, can form the perfect epitaxy single-crystal Graphene of lattice quality.
The invention provides a kind of method of heteroepitaxial growth Graphene, utilize plasma enhanced chemical vapor deposition method extending and growing graphene on single crystalline substrate, wherein the lattice of the lattice of this single crystalline substrate and Graphene is complementary.
According to method provided by the invention, wherein the material of this single crystalline substrate is selected from the group that comprises ruthenium (0001), iridium (111), palladium (111), rhodium (111), nickel (111), cobalt (111), platinum (111), silicon carbide, high oriented graphite and boron nitride.
According to method provided by the invention, wherein in the plasma enhanced chemical vapor deposition process, the gas that passes into is hydrocarbon polymer.
According to method provided by the invention, wherein said hydrocarbon polymer is one or more in methane, acetylene, the ethene.
According to method provided by the invention, wherein epitaxially grown underlayer temperature is 300 ℃-600 ℃.
According to method provided by the invention, wherein epitaxially grown underlayer temperature is 450 ℃-550 ℃.
According to method provided by the invention, wherein the air pressure during plasma enhanced chemical vapor deposition is less than 1Torr.
According to method provided by the invention, wherein the epitaxially grown time is 2-3 hour.
Method provided by the invention is used is outside carbon source but not carbon source on the substrate, temperature of reaction is low, less than 600 ℃, whole process does not have catalyzer, do not need the processing of subsequent catalyst, the size of the Graphene of generation is large, quality good, have higher specific conductivity, and the size of growth sample only is subjected to the restriction of PECVD cavity, can be in the SiC crystal column surface direct growth of 4 inches of sizes, cost is low, easy and simple to handle, controllability is good.
No matter method provided by the invention is the basic physics problem to the big area direct growth technology of exploring Graphene, the growth mechanism of understanding Graphene, research Graphene, or to the practical application of exploring graphene film, expand Graphene range of application all significant.
Description of drawings
Embodiments of the present invention is further illustrated referring to accompanying drawing, wherein:
Fig. 1 a is the scanning tunnel microscope morphology characterization according to the epitaxial graphite alkene of the method growth of embodiment 1;
Fig. 1 b be among Fig. 1 a at random the scanning tunnel microscope of the Atomic Resolution at a place characterize;
Fig. 2 a is according to the optical microscope image of the epitaxial graphite alkene of the method growth of embodiment 2;
Fig. 2 b be among Fig. 2 a at random the scanning tunnel microscope of the Atomic Resolution at a place characterize.
Embodiment
Utilize plasma enhanced chemical vapor deposition (PECVD) method, by the plasma decomposes hydrocarbon polymer, its ionization is become active group (CH
+, CH
2+, CH
3+Deng), at a certain temperature, in the mechanism of substrate surface according to nucleation-grow up-film forming, realize the direct growth of Graphene.At first in substrate surface nucleation at random, growth forms the Graphene island of tens nanometers of disperseing when low cover degree; Along with the increase of coverage, the Graphene island is grown up, and is seamless spliced between the adjacent island, finally forms continuous graphene film, covers whole substrate surface.
Method provided by the invention is to utilize plasma enhanced chemical vapor deposition (PECVD) technology to be implemented in extending and growing graphene on the various single crystalline substrate.Concrete principle is to utilize the plasma decomposes hydrocarbon polymer, and its ionization is become active group (CxHy, x, y=1,2,3......), under suitable growth temperature, these carbonaceous active group contacts also condense together, simultaneously, can be paired between active group inside or the active group slough the H atom, form simultaneously the C-C key, final H atom is sloughed fully, forms SP
2The C-C key of hydridization has namely formed the Graphene nucleus.Be subject to the impact of the smooth substrate surface of atomic level, all these little Graphene nucleus when forming, can be subject to the substrate surface lattice impact and with respect to the duplicate direction tiling of substrate surface lattice growth.Afterwards, more carbonaceous active group is aggregated to the Graphene nucleus edge of forming core, takes off H, forms SP
2The C-C key, Graphene is grown up.When growth to a certain degree the time, adjacent Graphene can be in contact with one another, they directly also can form SP by the C atom at edge
2The C-C key, all Graphenes of final substrate surface can be bonded with each other together, be grown to serve as continuous, be orientated consistent Graphene uniformly, everywhere.
Present embodiment provides a kind of method of heteroepitaxial growth Graphene, comprising:
1) the smooth high oriented graphite substrate of atomic level is put into the PECVD cavity, be evacuated down to 10
-3Torr, substrate are warmed up to 400 ℃;
2) pass into methane, form plasma body, the air pressure in the control PECVD cavity is 1Torr, and the power that makes plasma body is 120 watts, grows after 2 hours, stops process of growth;
3) continue to pass into methane as shielding gas, make simultaneously substrate drop to room temperature, then sample is taken out.
Fig. 1 a is the scanning tunnel microscope morphology characterization of the epitaxial graphite alkene that obtains of present embodiment.Can see that the first layer epitaxial graphite alkene has been grown to serve as one deck continuous thin film substantially, second layer Graphene has a small amount of forming core.Fig. 1 b be among Fig. 1 a at random the scanning tunnel microscope of the Atomic Resolution at a place characterize, can see that the atomic structure of epitaxial graphite alkene is graphene-structured, crystalline network is very perfect.
Embodiment 2
Present embodiment provides a kind of method of heteroepitaxial growth Graphene, comprising:
1) the smooth monocrystal SiC substrate of atomic level is put into the PECVD cavity, be evacuated down to 10
-3Torr, substrate are warmed up to 500 ℃;
2) pass into acetylene, form plasma body, the air pressure in the control PECVD cavity is 0.8Torr, and the power that makes plasma body is 100 watts, grows after 2 hours, stops process of growth;
3) continue to pass into acetylene as shielding gas, make simultaneously substrate drop to room temperature, then sample is taken out.
Fig. 2 a is the optical microscope image of the epitaxial graphite alkene that obtains of present embodiment, can see that the surface is very even, and wherein white oblique line is the step place of silicon carbide substrates itself, has before and after growth, and is under this growth temperature, unchanged before and after the growth.Fig. 2 b be on the substrate at random the scanning tunnel microscope of the Atomic Resolution of the epitaxial graphite alkene at a place characterize, can see that the lattice of epitaxial graphite alkene is very perfect.
Embodiment 3
Present embodiment provides a kind of method of heteroepitaxial growth Graphene, comprising:
1) the smooth monocrystalline BN substrate of atomic level is put into the PECVD cavity, be evacuated down to 10
-3Torr, substrate are warmed up to 600 ℃;
2) pass into ethene, form plasma body, the air pressure in the control PECVD cavity is 0.2Torr, and the power that makes plasma body is 50 watts, grows after 3 hours, stops process of growth;
3) continue to pass into ethene as shielding gas, make simultaneously substrate drop to room temperature, then sample is taken out.
Embodiment 4
Present embodiment provides a kind of method of heteroepitaxial growth Graphene, comprising:
1) the smooth ruthenium of atomic level (0001) substrate is put into the PECVD cavity, be evacuated down to 10
-3Torr, substrate are warmed up to 300 ℃;
2) pass into ethene, form plasma body, the air pressure in the control PECVD cavity is 0.5Torr, and the power that makes plasma body is 80 watts, grows after 3 hours, stops process of growth;
3) continue to pass into ethene as shielding gas, make simultaneously substrate drop to room temperature, then sample is taken out.
According to one embodiment of present invention, wherein the substrate of heteroepitaxial growth Graphene can be various precious metal substrates and monocrystalline silicon carbide, high oriented graphite and the boron nitride substrates such as ruthenium (0001), iridium (111), palladium (111), rhodium (111) nickel (111), cobalt (111), platinum (111), the lattice of these substrates and the lattice of Graphene are complementary, thereby can form the perfect epitaxial graphite alkene of crystalline network.
According to one embodiment of present invention, the gas that wherein forms plasma body can for hydrocarbon polymers such as methane, acetylene, ethene, also can be the mixed gas of above-mentioned gas.
According to one embodiment of present invention, wherein plasma power is 50-120 watt, can decide according to the air pressure of growing environment, and in general, air pressure is higher, and required plasma power is also higher.
According to one embodiment of present invention, wherein the underlayer temperature during epitaxy is 300 ℃-600 ℃, is preferably 450 ℃-550 ℃.
According to one embodiment of present invention, wherein the air pressure during epitaxy can be less than 1Torr.
According to one embodiment of present invention, wherein the epitaxially grown time decides according to needed film growth thickness, is generally 2-3 hour.
It should be noted last that above embodiment is only unrestricted in order to technical scheme of the present invention to be described.Although with reference to embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, technical scheme of the present invention is made amendment or is equal to replacement, do not break away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (9)
1. the method for a heteroepitaxial growth Graphene is utilized plasma enhanced chemical vapor deposition method extending and growing graphene on single crystalline substrate, and wherein the lattice of the lattice of this single crystalline substrate and Graphene is complementary.
2. method according to claim 1, wherein the material of this single crystalline substrate is selected from the group that comprises ruthenium (0001), iridium (111), palladium (111), rhodium (111), nickel (111), cobalt (111), platinum (111), silicon carbide, high oriented graphite and boron nitride.
3. method according to claim 1, wherein in the plasma enhanced chemical vapor deposition process, the gas that passes into is hydrocarbon polymer.
4. method according to claim 3, wherein said hydrocarbon polymer is one or more in methane, acetylene, the ethene.
5. method according to claim 1, wherein epitaxially grown underlayer temperature is 300 ℃-600 ℃.
6. method according to claim 5, wherein epitaxially grown underlayer temperature is 450 ℃-550 ℃.
7. method according to claim 1, wherein the air pressure during plasma enhanced chemical vapor deposition is less than 1Torr.
8. method according to claim 1, wherein the epitaxially grown time is 2-3 hour.
9. the formed Graphene of method one of according to claim 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110222191.2A CN102910614B (en) | 2011-08-04 | 2011-08-04 | Method for heterogeneous epitaxial growth of graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110222191.2A CN102910614B (en) | 2011-08-04 | 2011-08-04 | Method for heterogeneous epitaxial growth of graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102910614A true CN102910614A (en) | 2013-02-06 |
| CN102910614B CN102910614B (en) | 2015-04-22 |
Family
ID=47609225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110222191.2A Active CN102910614B (en) | 2011-08-04 | 2011-08-04 | Method for heterogeneous epitaxial growth of graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102910614B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812566A (en) * | 2012-11-26 | 2015-07-29 | 纳米技术仪器公司 | Unitary graphene layer or graphene single crystal |
| CN105019030A (en) * | 2014-04-28 | 2015-11-04 | 中国科学院物理研究所 | Highly-matched crystal orientation stacked structure of graphene and hexagonal boron nitride and preparation method of highly-matched crystal orientation stacked structure |
| CN107244666A (en) * | 2017-05-31 | 2017-10-13 | 山东大学 | A kind of method using hexagonal boron nitride as the point big domain graphene of seeded growth |
| CN110342502A (en) * | 2019-06-26 | 2019-10-18 | 上海交通大学 | A kind of preparation method of graphite flake growth in situ graphene complex carbon material |
| US11708271B2 (en) | 2015-12-15 | 2023-07-25 | Corning Incorporated | Method for producing a graphene film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798706A (en) * | 2009-02-10 | 2010-08-11 | 中国科学院物理研究所 | Method for extending and growing graphene on SiC substrate |
| CN102102220A (en) * | 2009-12-22 | 2011-06-22 | 中国科学院物理研究所 | Preparation method of graphene on diamond (111) surface |
| CN102103953A (en) * | 2009-12-22 | 2011-06-22 | 中国科学院物理研究所 | Cold cathode field emission material epitaxially growing on silicon carbide substrate and method |
-
2011
- 2011-08-04 CN CN201110222191.2A patent/CN102910614B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798706A (en) * | 2009-02-10 | 2010-08-11 | 中国科学院物理研究所 | Method for extending and growing graphene on SiC substrate |
| CN102102220A (en) * | 2009-12-22 | 2011-06-22 | 中国科学院物理研究所 | Preparation method of graphene on diamond (111) surface |
| CN102103953A (en) * | 2009-12-22 | 2011-06-22 | 中国科学院物理研究所 | Cold cathode field emission material epitaxially growing on silicon carbide substrate and method |
Non-Patent Citations (1)
| Title |
|---|
| J. J. WANG ET. AL.: "Free-standing subnanometer graphite sheets", 《APPLIED PHYSICS LETTERS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812566A (en) * | 2012-11-26 | 2015-07-29 | 纳米技术仪器公司 | Unitary graphene layer or graphene single crystal |
| CN105019030A (en) * | 2014-04-28 | 2015-11-04 | 中国科学院物理研究所 | Highly-matched crystal orientation stacked structure of graphene and hexagonal boron nitride and preparation method of highly-matched crystal orientation stacked structure |
| CN105019030B (en) * | 2014-04-28 | 2019-01-08 | 中国科学院物理研究所 | Height crystal orientation matching stacked structure of graphene/hexagonal boron nitride and preparation method thereof |
| US11708271B2 (en) | 2015-12-15 | 2023-07-25 | Corning Incorporated | Method for producing a graphene film |
| CN107244666A (en) * | 2017-05-31 | 2017-10-13 | 山东大学 | A kind of method using hexagonal boron nitride as the point big domain graphene of seeded growth |
| CN107244666B (en) * | 2017-05-31 | 2020-04-21 | 山东大学 | Method for growing large-domain graphene by taking hexagonal boron nitride as point seed crystal |
| CN110342502A (en) * | 2019-06-26 | 2019-10-18 | 上海交通大学 | A kind of preparation method of graphite flake growth in situ graphene complex carbon material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102910614B (en) | 2015-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102260858B (en) | Method for directly growing graphine on various substrates | |
| CN102933491B (en) | The production method of Graphene | |
| US9812527B2 (en) | Growth of semiconductors on hetero-substrates using graphene as an interfacial layer | |
| Nyakiti et al. | Enabling graphene-based technologies: Toward wafer-scale production of epitaxial graphene | |
| KR101284059B1 (en) | Graphene-Oxide Semiconductor Heterojunction Devices, and Production Method of the Same | |
| US20140374960A1 (en) | Method for producing a graphene film | |
| CN104334495A (en) | Methods of growing uniform, large-scale, multilayer graphene films | |
| CN102910614B (en) | Method for heterogeneous epitaxial growth of graphene | |
| KR101105249B1 (en) | Method of forming graphene pattern utilizing imprint | |
| JP2003298077A (en) | Solar cell | |
| US10017878B2 (en) | Growth method of graphene | |
| KR20110064164A (en) | Method of forming graphene layer using chemical vapor deposition | |
| US9287116B2 (en) | Method of forming multilayer graphene structure | |
| Tokuda | Homoepitaxial diamond growth by plasma-enhanced chemical vapor deposition | |
| KR101294362B1 (en) | Method for graphene hybrid film comprising hexagonal boron nitride | |
| CN109841497A (en) | A kind of method, gallium nitride material and the application of isoepitaxial growth gallium nitride | |
| Liu et al. | Chemical vapor deposition graphene of high mobility by gradient growth method on an 4H-SiC (0 0 0 1) substrate | |
| Ma et al. | Progress of graphene growth on copper by chemical vapor deposition: Growth behavior and controlled synthesis | |
| TW201434744A (en) | Method for manufacturing graphene film and graphene channel of transistor | |
| KR101466482B1 (en) | Etching-free graphene growth method using oxidizable metal | |
| CN107244666B (en) | Method for growing large-domain graphene by taking hexagonal boron nitride as point seed crystal | |
| KR101308120B1 (en) | Method for manufacturing graphene with controlling a direction of growth | |
| CN108892132A (en) | Prepare auxiliary device, the graphene and preparation method thereof of graphene | |
| Lebedev et al. | Formation of nanocarbon films on the SiC surface through sublimation in vacuum | |
| CN107500277B (en) | Graphene boundary regulation and control method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |